CN1500722A - Method for preparing MCM-22 molecular sieves - Google Patents

Method for preparing MCM-22 molecular sieves Download PDF

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Publication number
CN1500722A
CN1500722A CNA021452334A CN02145233A CN1500722A CN 1500722 A CN1500722 A CN 1500722A CN A021452334 A CNA021452334 A CN A021452334A CN 02145233 A CN02145233 A CN 02145233A CN 1500722 A CN1500722 A CN 1500722A
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mcm
sio
molecular sieve
crystallization
template
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CN1207199C (en
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高焕新
周斌
顾瑞芳
方华
季树芳
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to the preparation process of MCM-22 molecular sieve and solves the problems in the preparation process, including high synthesis cost and environmental pollution. The technological scheme of the present invention is that during the preparation of MCM-22 molecular sieve, partial or all the template agent comes from MCM-22 molecular sieve crystallizing mother liquid. The present invention may be used in industrial preparation.

Description

The preparation method of MCM-22 molecular sieve
Technical field
The present invention relates to the preparation method of MCM-22 molecular sieve.
Background technology
The MCM-22 molecular sieve is the novel catalytic material that plays report in nineteen ninety.It has two kinds of independently ten-ring pore canal system, and wherein a kind of inside of system comprises the large-scale supercage of 0.71 nanometer * 0.71 nanometer * 1.82 nanometers.These supercages are stacked on above another by overlapping one of six-ring, are applied in the window of approximate ellipsoidal ten-ring.Another kind of pore canal system forms two-dimentional sinusoidal waveform duct, on every side round the coincidence six-ring that links to each other with supercage.Because MCM-22 has the pore passage structure different with molecular sieve in the past, unusual thermostability and high-ratio surface, thereby crucial application is arranged in Industrial Catalysis.Such as in propylene and benzene preparing isopropylbenzene technology, can utilize the extraordinary selectivity of MCM-22 molecular sieve to replace solid phosphoric acid catalyst, improve the productive rate of isopropyl benzene in the catalytic process etc. greatly.
The method of at present synthetic MCM-22 mainly is a hydrothermal crystallization method.Document US 4954325 has been introduced a kind of composition and preparation and purposes of crystal formation material, and it is to make template R with hexamethylene imine, and the mol ratio of its silicon source, aluminium source, alkali, template and water is:
SiO 2/Al 2O 3＝10～60
OH -/SiO 2＝0.1～0.5
R/SiO 2＝0.1～0.5
M/SiO 2＝0.1～1.0
H 2O/SiO 2＝10～50
At crystallization temperature is 80～225 ℃, and crystallization time is a synthetic MCM-22 molecular sieve under 1～60 day condition.The silica alumina ratio of the synthetic MCM-22 of this piece patent institute is not high, and find from embodiment, its crystallization time is longer, generally need 6～7 days, in addition because template six subunit imines prices are more expensive, cause molecular sieve preparation cost height, and itrogenous organic substance pollutes easily to environment in the crystalline mother solution.
Summary of the invention
Technical problem to be solved by this invention is to have in the document in order to overcome in the past that itrogenous organic substance causes environmental pollution problems in preparation MCM-22 molecular sieve cost height and the crystalline mother solution, and a kind of preparation method of new MCM-22 molecular sieve is provided.It is low that this method has a MCM-22 molecular sieve preparation cost, characteristics relatively more friendly to environment in the preparation process.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of MCM-22 molecular sieve, at first count your ratio of silicon source, aluminium source, alkali, template and hydromassage: SiO 2/ Al 2O 3Be 5～200, OH -/ SiO 2Be 0.10～1.0, H 2O/SiO 2Be 5～200, R/SiO 2It is 0.05～1.0 mixed, wherein R is a template, be selected from least a of pentamethylene imines, hexamethylene imine or heptamethylene imines, with said mixture is under 120～180 ℃ of conditions at crystallization temperature under agitation, crystallization time is 5～240 hours, fractional crystallization product and reclaim mother liquor then, crystallized product makes the MCM-22 molecular sieve through washing, drying, and wherein part or all of template is from MCM-22 crystallization of molecular sieves mother liquor.
In the technique scheme in the mixture with molar ratio computing preferable range: SiO 2/ Al 2O 3Be 20～80, OH -/ SiO 2Be 0.10～0.5, H 2O/SiO 2Be 10～60, R/SiO 2Be 0.1～0.6.The silicon source is selected from least a in soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; The aluminium source is selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, aluminum oxide, kaolin, pseudo-boehmite or the polynite; Alkali is mineral alkali, is selected from alkali metal hydroxide, specifically can be at least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.The preferable range of crystallization temperature is 140～160 ℃, and the crystallization time preferable range is 30～60 hours.In the synthetic MCM-22 molecular sieve, preferred version is a MCM-22 crystallization of molecular sieves mother liquor of recycling recovery, template total amount mol ratio is 0.1～0.8 in template in the MCM-22 crystallization of molecular sieves mother liquor that reclaims and the MCM-22 molecular sieve precursor, and preferable range is 0.1～0.5.
Key of the present invention is to recycle the crystallization of molecular sieves mother liquor in the raw mix to come synthesis of molecular sieve, reaches to reduce the molecular sieve preparation cost, reduces the purpose of polluting.
The present invention has reduced molecular sieve and has synthesized cost owing to adopted the crystallization of molecular sieves mother liquor that reclaims synthesize the MCM-22 molecular sieve in building-up process, has eliminated in the crystallization mother liquor nitrogenous organic liquid waste simultaneously to the pollution of environment.The X diffracted ray collection of illustrative plates of the MCM-22 molecular sieve that makes is as follows:
D (A) relative intensity I/I 0
30.0 ±2.2 W-M
22.1 ±1.3 W
6.00 ±0.10 W-M
4.64 ±0.08 W
4.06 ±0.07 W-S
3.91 ±0.07 M-VS
Obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With sodium aluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 990 gram water, add sodium hydroxide 6.18 grams and make it dissolving, add organic amine template hexamethylene imine 49.5 grams then under condition of stirring, add silicon sol (SiO again 240 weight %) 150 grams, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝20
OH -/SiO 2＝0.3
R/SiO 2＝0.5
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 30 hours.Cooling then, the solid product of filtering for crystallizing, and reclaim crystalline mother solution.Above-mentioned solid crystallized product more after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 18.7.
[embodiment 2]
With sodium aluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 500 gram water, add sodium hydroxide 6.18 grams and make it dissolving, under condition of stirring, add organic amine template hexamethylene imine 39.6 grams and 499.9 grams then and contain the crystalline mother solution that hexamethylene imine 9.9 restrains, add silicon sol (SiO again 240 weight %) 150 grams, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝20
OH -/SiO 2＝0.3
R/SiO 2＝0.5
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 30 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 19.3.
[embodiment 3]
With sodium aluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 500 gram water, add sodium hydroxide 18.18 grams and make it dissolving, under condition of stirring, add organic amine template hexamethylene imine 59.5 grams and 2648.5 grams then and contain the crystalline mother solution that hexamethylene imine 178.5 restrains, add silicon sol (SiO again 240 weight %) 450.7 grams, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝60
OH -/SiO 2＝0.2
R/SiO 2＝0.8
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 50 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 52.
[embodiment 4]
With sodium aluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 1500 gram water, add sodium hydroxide 18.18 grams and make it dissolving, under condition of stirring, add organic amine template hexamethylene imine 118.8 grams and 2458.2 grams then and contain the crystalline mother solution that hexamethylene imine 178.2 restrains, add silicon sol (SiO again 240 weight %) 901 grams, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝120
OH -/SiO 2＝0.1
R/SiO 2＝0.5
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 45 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 114.3.
[embodiment 5]
With sodium aluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 1500 gram water, add sodium hydroxide 74.2 grams and make it dissolving, add the crystalline mother solution that 2649 grams contain organic amine template hexamethylene imine 99 grams then under condition of stirring, add silicon sol (SiO again 240 weight %) 750 grams, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝100
OH -/SiO 2＝0.4
R/SiO 2＝0.2
H 2O/SiO 2＝50
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 160 ℃ of crystallization 60 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 89.7, the degree of crystallinity 99.3% of MCM-22 molecular sieve.
[embodiment 6]
The organic formwork agent that uses is Azacyclooctane (heptamethylene imines).The order of adding raw material and ageing treatment condition are with reference to the scheme of embodiment 1, and it is 50 hours and material proportion (mol ratio) SiO with crystallization time that crystallization temperature is 150 ℃ 2/ Al 2O 3Be 25, template all comes from crystalline mother solution, and all the other are with embodiment 1, and it is the MCM-22 molecular sieve that products therefrom is carried out XRD determining.
[comparative example]
Sodium aluminate (Al 2O 343.5 weight %, Na 2O32.2 weight %) 12.86 grams are dissolved in the aqueous sodium hydroxide solution of 12.8 grams 50%, add 57.6 gram hexamethylene imines, add 109.4 gram precipitated silica (SiO in gained solution 290 weight %), the mol ratio of reaction mixture is:
SiO 2/Al 2O 3＝30
OH -/SiO 2＝0.18
R/SiO 2＝0.35
H 2O/SiO 2＝45
R is a hexamethylene imine.Mixture in 150 ℃ of following crystallization 30 hours, takes out part with product in the stainless steel crystallizing kettle, washing, and 110 ℃ of dryings, the XRD determining product is amorphous.Continue crystallization to 7 day, product is taken out, washing, 110 ℃ of dryings are MCM-22 through the XRD determining product.

Claims (7)

1, a kind of preparation method of MCM-22 molecular sieve at first counts your ratio of silicon source, aluminium source, alkali, template and hydromassage: SiO 2/ Al 2O 3Be 5～200, OH -/ SiO 2Be 0.10～1.0, H 2O/SiO 2Be 5～200, R/SiO 2It is 0.05～1.0 mixed, wherein R is a template, be selected from least a of pentamethylene imines, hexamethylene imine or heptamethylene imines, with said mixture is under 120～180 ℃ of conditions at crystallization temperature under agitation, crystallization time is 5～240 hours, fractional crystallization product and reclaim mother liquor then, crystallized product makes the MCM-22 molecular sieve through washing, drying, and part or all that it is characterized in that template is from MCM-22 crystallization of molecular sieves mother liquor.
2,, it is characterized in that in the mixture with molar ratio computing: SiO according to the preparation method of the described MCM-22 molecular sieve of claim 1 2/ Al 2O 3Be 20～80, OH -/ SiO 2Be 0.10～0.5, H 2O/SiO 2Be 10～60, R/SiO 2Be 0.1～0.6.
3,, it is characterized in that the silicon source is selected from least a in soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass according to the preparation method of the described MCM-22 molecular sieve of claim 1; The aluminium source is selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, aluminum oxide, kaolin, pseudo-boehmite or the polynite; Alkali is that mineral alkali is selected from alkali metal hydroxide.
4, according to the preparation method of the described MCM-22 molecular sieve of claim 1, it is characterized in that crystallization temperature is 140～160 ℃, crystallization time is 30～60 hours.
5,, it is characterized in that recycling the synthetic MCM-22 molecular sieve of MCM-22 crystallization of molecular sieves mother liquor of recovery according to the preparation method of the described MCM-22 molecular sieve of claim 1.
6, according to the synthetic method of the described MCM-22 molecular sieve of claim 1, template total amount mol ratio is 0.1～0.8 in template in the MCM-22 crystallization of molecular sieves mother liquor that it is characterized in that reclaiming and the MCM-22 molecular sieve precursor.
7, according to the synthetic method of the described MCM-22 molecular sieve of claim 6, template total amount mol ratio is 0.1～0.5 in template in the MCM-22 crystallization of molecular sieves mother liquor that it is characterized in that reclaiming and the MCM-22 molecular sieve precursor.
CN 02145233 2002-11-13 2002-11-13 Method for preparing MCM-22 molecular sieves Expired - Lifetime CN1207199C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328165C (en) * 2005-04-18 2007-07-25 华东师范大学 Method for preparing MCM-22, molecular sieve
CN100341784C (en) * 2004-12-17 2007-10-10 中国科学院大连化学物理研究所 Synthetic method for MCM-22 molecular sieve
CN100363259C (en) * 2004-12-23 2008-01-23 中国科学院大连化学物理研究所 Method for preparing MCM-22 molecular sieve in high silicon
CN101384365A (en) * 2006-02-14 2009-03-11 埃克森美孚化学专利公司 Method of preparing a molecular sieve composition
CN101003022B (en) * 2007-01-19 2010-05-19 中国石油化工股份有限公司 Method for synthesizing MCM-22 molecular sieve catalyst
CN102190312A (en) * 2010-03-18 2011-09-21 华东师范大学 Method for recycling molecular sieve mother solution
CN102311127A (en) * 2010-07-07 2012-01-11 中国石油化工股份有限公司 Method for preparing small-grain MCM-22 molecular sieve
WO2012070067A2 (en) * 2010-11-23 2012-05-31 Reliance Industries Ltd. A method for the preparation of mww type zeolite

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100341784C (en) * 2004-12-17 2007-10-10 中国科学院大连化学物理研究所 Synthetic method for MCM-22 molecular sieve
CN100363259C (en) * 2004-12-23 2008-01-23 中国科学院大连化学物理研究所 Method for preparing MCM-22 molecular sieve in high silicon
CN1328165C (en) * 2005-04-18 2007-07-25 华东师范大学 Method for preparing MCM-22, molecular sieve
CN101384365A (en) * 2006-02-14 2009-03-11 埃克森美孚化学专利公司 Method of preparing a molecular sieve composition
CN101384365B (en) * 2006-02-14 2012-02-08 埃克森美孚化学专利公司 Method of preparing a molecular sieve composition
CN102527428A (en) * 2006-02-14 2012-07-04 埃克森美孚化学专利公司 Method of preparing a molecular sieve composition
CN102527428B (en) * 2006-02-14 2014-11-26 埃克森美孚化学专利公司 Method of preparing a molecular sieve composition
CN101003022B (en) * 2007-01-19 2010-05-19 中国石油化工股份有限公司 Method for synthesizing MCM-22 molecular sieve catalyst
CN102190312A (en) * 2010-03-18 2011-09-21 华东师范大学 Method for recycling molecular sieve mother solution
CN102311127B (en) * 2010-07-07 2013-06-19 中国石油化工股份有限公司 Method for preparing small-grain MCM-22 molecular sieve
CN102311127A (en) * 2010-07-07 2012-01-11 中国石油化工股份有限公司 Method for preparing small-grain MCM-22 molecular sieve
WO2012070067A2 (en) * 2010-11-23 2012-05-31 Reliance Industries Ltd. A method for the preparation of mww type zeolite
CN103384644A (en) * 2010-11-23 2013-11-06 信实工业公司 A method for the preparation of MWW type zeolite
WO2012070067A3 (en) * 2010-11-23 2012-07-19 Reliance Industries Ltd. Preparation method of mww type zeolite
US9359216B2 (en) 2010-11-23 2016-06-07 Reliance Industries Limited Method for the preparation of MWW type zeolite
CN103384644B (en) * 2010-11-23 2016-10-26 信实工业公司 A kind of preparation method of MWW type zeolite

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